| 1. |
- Zheng, Qian, et al.
(författare)
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Constructing InP/ZnSe Quantum Dots with Shell Gradient In3+ Doping for Photoelectrochemical Cells
- 2024
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Ingår i: ACS Energy Letters. - 2380-8195. ; 9:5, s. 2358-2366
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Tidskriftsartikel (refereegranskat)abstract
- Environmentally friendly InP/ZnSe core/shell quantum dots (QDs) with high absorption coefficients and tunable band gaps have demonstrated great potential for photoelectrochemical (PEC) water splitting. However, the tightly bound excitonic feature by inherent type I band alignment tends to reduce the charge separation efficiency, limiting their PEC performance. Herein, we devised heterovalent In3+ gradient doping in the ZnSe shell of InP QD to construct core/shell structural InP/ZnSe-G-In QDs. The In3+ dopant increased the Fermi level of the ZnSe shell; thus continuous semiconductor homojunction and band bending were formed by gradient composition doping, which accelerates the exciton separation through the built-in electric field. As a result, the PEC cells based on such QDs exhibited high photocurrent density of 8.7 mA/cm2, demonstrating one of the highest values for the InP-based QDs PEC cells. This work provides an effective strategy for the application of type I band structure QDs in solar energy conversion.
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| 2. |
- Cao, Yuehan, et al.
(författare)
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Dual Functions of O-Atoms in the g-C3N4/BO0.2N0.8Interface : Oriented Charge Flow In-Plane and Separation within the Interface to Collectively Promote Photocatalytic Molecular Oxygen Activation
- 2020
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 12:30, s. 34432-34440
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Tidskriftsartikel (refereegranskat)abstract
- The photocatalytic performance of two-dimensional materials is largely limited by the fast recombination of photogenerated charges. Herein, we design and fabricate a novel g-C3N4/BO0.2N0.8 van der Waals heterostructure to realize oriented charge flow in-plane and separation within the interface. On one hand, a B-C bond forms within the g-C3N4/BO0.2N0.8 interface after the introduction of O atoms. The B-C bond as the mediator bridges g-C3N4 and BO0.2N0.8 sides to enhance the effective separation of photogenerated charges. On the other hand, the existence of O atoms promotes the formation of a B-O-O-B intermediate to realize that molecular oxygen can directionally obtain electrons from the surface to generate O2-. As a result, BO0.2N0.8 instead of g-C3N4 is considered to be the main reaction side, and the energy barrier of NO3- generation is significantly decreased. The NO removal performance of g-C3N4/BO0.2N0.8 is enhanced and the NO2 generation is effectively controlled compared with that of g-C3N and g-C3N4/BN. This work could provide an effective and facile strategy to tune oriented charge transfer.
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| 3. |
- Huang, Zheng, et al.
(författare)
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Constructing type-II CuInSe2/CuInS2 core/shell quantum dots for high-performance photoelectrochemical cells
- 2024
-
Ingår i: SCIENCE CHINA Materials. - 2095-8226. ; 67:1, s. 134-142
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Tidskriftsartikel (refereegranskat)abstract
- CuInSe2 (CISe) quantum dots (QDs) have shown promising applications in photoelectrochemical (PEC) cells due to their nontoxicity, high extinction coefficient, and wide optical absorption range; however, their low PEC performance prevents their applications due to insufficient charge carrier separation and severe charge recombination. Herein, CISe/CuInS2 (CISe/CIS) core/shell structured QDs are designed and constructed to promote charge separation and diminish interface defects. Afterward, the copper vacancy (VCu) state of CISe/CIS QDs is enriched by modulating the precursor molar ratios of In/Cu. Therefore, the radiative recombination of the conduction band edge electrons with the VCu localized holes becomes dominant and prolongs the carrier lifetime compared with intrinsic band-to-band recombination, thus promoting charge separation. Consequently, the VCu-rich CISe/CIS QD-based photoanode shows a high photocurrent density of 8.0 mA cm−2, which is one of the highest values reported for CISe QD-based PEC cells. This work provides an effective approach for promoting charge carrier separation and transfer through surface or intrinsic defect mediation for PEC applications of I–III–VI semiconductor nanocrystals.
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| 4. |
- Karlsson, Max, et al.
(författare)
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Mixed halide perovskites for spectrally stable and high-efficiency blue light-emitting diodes
- 2021
-
Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 12:1
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Tidskriftsartikel (refereegranskat)abstract
- Bright and efficient blue emission is key to further development of metal halide perovskite light-emitting diodes. Although modifying bromide/chloride composition is straightforward to achieve blue emission, practical implementation of this strategy has been challenging due to poor colour stability and severe photoluminescence quenching. Both detrimental effects become increasingly prominent in perovskites with the high chloride content needed to produce blue emission. Here, we solve these critical challenges in mixed halide perovskites and demonstrate spectrally stable blue perovskite light-emitting diodes over a wide range of emission wavelengths from 490 to 451 nanometres. The emission colour is directly tuned by modifying the halide composition. Particularly, our blue and deep-blue light-emitting diodes based on three-dimensional perovskites show high EQE values of 11.0% and 5.5% with emission peaks at 477 and 467 nm, respectively. These achievements are enabled by a vapour-assisted crystallization technique, which largely mitigates local compositional heterogeneity and ion migration.
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| 5. |
- Liu, Yang, et al.
(författare)
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Defect State Assisted Z-scheme Charge Recombination in Bi2O2CO3/Graphene Quantum Dot Composites for Photocatalytic Oxidation of NO
- 2020
-
Ingår i: ACS Applied Nano Materials. - : American Chemical Society (ACS). - 2574-0970. ; 3:1, s. 772-781
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Tidskriftsartikel (refereegranskat)abstract
- In this work, we explored the photoinduced charge carriers dynamics rationalizing the photocatalytic oxidation of NO over N-doped Bi2O2CO3/graphene quantum dots composites(N-BOC/GQDs) via time-resolved photoluminescence (TRPL). Under visible light illumination, only GQDs can be photoexcited and inject electrons to N-BOC within 0.5 ns. Under UV light irradiation, the interfacial Z-scheme heterojunction recombination between the electrons in N-BOC and holes in GQDs dominate the depopulation of excited states within 0.36 ns. Such efficient Z-scheme recombination regardless of the large energy difference (1.66 eV) is mediated by the interfacial oxygen vacany defect states characterized by both density functional theory calculations (DFT) and electron paramagnetic resonance (EPR) measurement. This finding provide a novel strategic view to improve the photocatalytic performance of the nanocomposite by interfacial engineering
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| 6. |
- Zou, Yatao, et al.
(författare)
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Manipulating crystallization dynamics through chelating molecules for bright perovskite emitters
- 2021
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 12:1
-
Tidskriftsartikel (refereegranskat)abstract
- Molecular additives are widely utilized to minimize non-radiative recombination in metal halide perovskite emitters due to their passivation effects from chemical bonds with ionic defects. However, a general and puzzling observation that can hardly be rationalized by passivation alone is that most of the molecular additives enabling high-efficiency perovskite light-emitting diodes (PeLEDs) are chelating (multidentate) molecules, while their respective monodentate counterparts receive limited attention. Here, we reveal the largely ignored yet critical role of the chelate effect on governing crystallization dynamics of perovskite emitters and mitigating trap-mediated non-radiative losses. Specifically, we discover that the chelate effect enhances lead-additive coordination affinity, enabling the formation of thermodynamically stable intermediate phases and inhibiting halide coordination-driven perovskite nucleation. The retarded perovskite nucleation and crystal growth are key to high crystal quality and thus efficient electroluminescence. Our work elucidates the full effects of molecular additives on PeLEDs by uncovering the chelate effect as an important feature within perovskite crystallization. As such, we open new prospects for the rationalized screening of highly effective molecular additives.
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| 7. |
- Alvarez, Sol Gutierrez, et al.
(författare)
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Charge Carrier Diffusion Dynamics in Multisized Quaternary Alkylammonium-Capped CsPbBr3 Perovskite Nanocrystal Solids
- 2021
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 13:37, s. 44742-44750
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Tidskriftsartikel (refereegranskat)abstract
- CsPbBr3 quantum dots (QDs) are promising candidates for optoelectronic devices. The substitution of oleic acid ( OA) and oleylamine ( OLA) capping agents with a quaternary alkylammonium such as di-dodecyl dimethyl ammonium bromide (DDAB) has shown an increase in external quantum efficiency (EQE) from 0.19% (OA/OLA) to 13.4% (DDAB) in LED devices. The device performance significantly depends on both the diffusion length and the mobility of photoexcited charge carriers in QD solids. Therefore, we investigated the charge carrier transport dynamics in DDAB-capped CsPbBr3 QD solids by constructing a bi-sized QD mixture film. Charge carrier diffusion can be monitored by quantitatively varying the ratio between two sizes of QDs, which varies the mean free path of the carriers in each QD cluster. Excited-state dynamics of the QD solids obtained from ultrafast transient absorption spectroscopy reveals that the photogenerated electrons and holes are difficult to diffuse among small-sized QDs (4 nm) due to the strong quantum confinement. On the other hand, both photoinduced electrons and holes in large-sized QDs (10 nm) would diffuse toward the interface with the small-sized QDs, followed by a recombination process. Combining the carrier diffusion study with a Monte Carlo simulation on the QD assembly in the mixture films, we can calculate the diffusion lengths of charge carriers to be similar to 239 +/- 16 nm in 10 nm CsPbBr3 QDs and the mobility values of electrons and holes to be 2.1 (+/- 0.1) and 0.69 (+/- 0.03) cm(2)/V s, respectively. Both parameters indicate an efficient charge carrier transport in DDAB-capped QD films, which rationalized the perfect performance of their LED device application.
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| 8. |
- Alvarez, Sol Laura Gutierrez, et al.
(författare)
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Morphology-Dependent One- and Two-Photon Absorption Properties in Blue Emitting CsPbBr3Nanocrystals
- 2022
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Ingår i: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 13:22, s. 4897-4904
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Tidskriftsartikel (refereegranskat)abstract
- The linear and nonlinear optical parameters and morphologic dependence of CsPbBr3 nanocrystals (NCs) are crucial for device engineering. In particular, such information in asymmetric nanocrystals is still insufficient. We characterized the OPLA (σ1) and TPA cross sections (σ2) of a series CsPbBr3 nanocrystals with various aspect ratios (AR) using femtosecond transient absorption spectroscopy (TAS). The σ1 presents a linear volume dependence of all the samples, which agrees with the previous behavior in CsPbBr3 QDs. However, the σ2 values do not exhibit conventional power dependency of the crystal volume but are also modulated by the shape-dependent local field factors. In addition, the local field effect in CsPbBr3 NCs is contributed by their asymmetric morphologies and polar ionic lattices, which is more pronounced than in conventional semiconductor NCs. Finally, we revealed that the lifetimes of photogenerated multiexcitonic species of those nanocrystals feature identical morphology independence in both OPLA and TPA.
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| 9. |
- Canton, Sophie E., et al.
(författare)
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Ultrafast Jahn-Teller Photoswitching in Cobalt Single-Ion Magnets
- 2023
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Ingår i: Advanced Science. - 2198-3844. ; 10:21
-
Tidskriftsartikel (refereegranskat)abstract
- Single-ion magnets (SIMs) constitute the ultimate size limit in the quest for miniaturizing magnetic materials. Several bottlenecks currently hindering breakthroughs in quantum information and communication technologies could be alleviated by new generations of SIMs displaying multifunctionality. Here, ultrafast optical absorption spectroscopy and X-ray emission spectroscopy are employed to track the photoinduced spin-state switching of the prototypical complex [Co(terpy)2]2+ (terpy = 2,2′:6′,2″-terpyridine) in solution phase. The combined measurements and their analysis supported by density functional theory (DFT), time-dependent-DFT (TD-DFT) and multireference quantum chemistry calculations reveal that the complex undergoes a spin-state transition from a tetragonally elongated doublet state to a tetragonally compressed quartet state on the femtosecond timescale, i.e., it sustains ultrafast Jahn-Teller (JT) photoswitching between two different spin multiplicities. Adding new Co-based complexes as possible contenders in the search for JT photoswitching SIMs will greatly widen the possibilities for implementing magnetic multifunctionality and eventually controlling ultrafast magnetization with optical photons.
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| 10. |
- Cao, Kequan, et al.
(författare)
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Constructing ZnTe Spherical Quantum Well for Efficient Light Emission
- 2024
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Ingår i: Nano Letters. - 1530-6984. ; 24:17, s. 5238-5245
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Tidskriftsartikel (refereegranskat)abstract
- ZnTe colloidal semiconductor nanocrystals (NCs) have shown promise for light-emitting diodes (LEDs) and displays, because they are free from toxic heavy metals (Cd). However, so far, their low photoluminescence (PL) efficiency (∼30%) has hindered their applications. Herein, we devised a novel structure of ZnTe NCs with the configuration of ZnSe (core)/ZnTe (spherical quantum well, SQW)/ZnSe (shell). The inner layer ZnTe was grown at the surface of ZnSe core with avoiding using highly active and high-risk Zn sources. Due to the formation of coherently strained heterostructure which reduced the lattice mismatch, and the thermodynamic growth of ZnTe, the surface or interface defects were suppressed. A high PL efficiency of >60% was obtained for the green light-emitting ZnSe/ZnTe/ZnSe SQWs after ZnS outer layer passivation, which is the highest value for colloidal ZnTe-based NCs. This work paves the way for the development of novel semiconductor NCs for luminescent and display applications.
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| 11. |
- Cao, Yuehan, et al.
(författare)
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Modulating electron density of vacancy site by single Au atom for effective CO2 photoreduction
- 2021
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 12:1
-
Tidskriftsartikel (refereegranskat)abstract
- The surface electron density significantly affects the photocatalytic efficiency, especially the photocatalytic CO2 reduction reaction, which involves multi-electron participation in the conversion process. Herein, we propose a conceptually different mechanism for surface electron density modulation based on the model of Au anchored CdS. We firstly manipulate the direction of electron transfer by regulating the vacancy types of CdS. When electrons accumulate on vacancies instead of single Au atoms, the adsorption types of CO2 change from physical adsorption to chemical adsorption. More importantly, the surface electron density is manipulated by controlling the size of Au nanostructures. When Au nanoclusters downsize to single Au atoms, the strong hybridization of Au 5d and S 2p orbits accelerates the photo-electrons transfer onto the surface, resulting in more electrons available for CO2 reduction. As a result, the product generation rate of AuSA/Cd1−xS manifests a remarkable at least 113-fold enhancement compared with pristine Cd1−xS.
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| 12. |
- Dan, Meng, et al.
(författare)
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A dual-interfacial system with well-defined spatially separated redox-sites for boosting photocatalytic overall H2S splitting
- 2021
-
Ingår i: Chemical Engineering Journal. - : Elsevier BV. - 1385-8947. ; 423
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Tidskriftsartikel (refereegranskat)abstract
- Integration of high activity, selectivity, and stability is urgently desired to achieve more ideal photocatalysts. Herein, we reported the rational design of MoS2-MnS@(InxCu1-x)2S3 (M-M@IC) catalysts with dual interface to integrate separated redox sites for boosting photocatalytic hydrogen sulphide (H2S) splitting and the resource utilization of sacrificial reagents (Na2S/Na2SO3). The spatially separated reduction (MnS) and oxidation (In2S3) sites in MnS/In2S3 heterojunction, on which MoS2 and Cu were selectively loaded, can drive electrons and holes near the surface to flow along opposite directions, while the heterojunction between MnS and In2S3 inhibits the bulk charge recombination. Furthermore, the introduction of Cu atoms creates a d-band center, which favours mass diffusion of reactants/products species and greatly facilitates sunlight response. The MoS2 serves to provide abundant sites for proton reduction due to the unsaturated-sulfur-edge-rich (US-rich) nature. As a result, the M−M@IC shows a state-of-the-art visible-light photocatalytic H2 evolution rate (126.5 mmol g-1h−1), inspiring stability of >50 h, and nearly 100% selectivity toward value-added Na2S2O3 production under optimized condition. This work opens up new opportunities for the construction and design of spatially separated catalytic site in photocatalysts.
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| 13. |
- Dan, Meng, et al.
(författare)
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Beyond hydrogen production : Solar−driven H2S−donating value−added chemical production over MnxCd1−xS/CdyMn1−yS catalyst
- 2021
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Ingår i: Applied Catalysis B: Environmental. - : Elsevier BV. - 0926-3373. ; 284
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Tidskriftsartikel (refereegranskat)abstract
- Simultaneous hydrogen (H2) evolution and value−added chemicals production are highly attractive but have not drawn enough attention. Here, we demonstrate a hydrogen sulphide (H2S)−induced product−targeting (HIPT) strategy for the coproduction of H2 and valuable chemical feedstocks from Na2S/Na2SO3 via overall H2S splitting using a MnxCd1−xS/CdyMn1−yS catalyst driven by visible light excitation. With this chemistry, 113 mmol g−1 h−1 of hydrogen evolution rate is achieved, surpassing most of the previously reported state-of-the-art photocatalyst, together with the production of value−added Na2S2O3 with nearly 100% selectivity. This work not only provides a good example for solar energy conversion via overall H2S splitting, but also offers new insights into the resource utilization of sacrificial donor (Na2S/Na2SO3) in various catalytic fields such as H2O splitting and CO2 reduction.
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| 14. |
- Elsayed, Mohamed Hammad, et al.
(författare)
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Visible-light-driven hydrogen evolution using nitrogen-doped carbon quantum dot-implanted polymer dots as metal-free photocatalysts
- 2021
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Ingår i: Applied Catalysis B: Environmental. - : Elsevier BV. - 0926-3373. ; 283
-
Tidskriftsartikel (refereegranskat)abstract
- Given the photocatalytic properties of semiconducting polymers and carbon quantum dots (CQDs), we report a new structure for a metal-free photocatalytic system with a promising efficiency for hydrogen production through the combination of an organic semiconducting polymer (PFTBTA) and N-doped carbon quantum dots (NCQDs) covered by PS-PEGCOOH to produce heterostructured photocatalysts in the form of polymer dots (Pdots). This design could provide strong interactions between the two materials owing to the space confinement effect in nanometer-sized Pdots. Small particle size NCQDs are easy to insert inside the Pdot, which leads to an increase in the stability of the Pdot structure and enhances the hydrogen evolution rate by approximately 5-fold over that of pure PFTBTA Pdots. The photophysics and the mechanism behind the catalytic activity of our design are investigated by transient absorption measurement, demonstrating the role of NCQDs to enhance the charge separation and the photocatalytic efficiency of the PFTBTA Pdot.
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| 15. |
- Geng, Huifang, et al.
(författare)
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Controlled synthesis of highly stable lead-free bismuth halide perovskite nanocrystals : tructures and photophysics
- 2023
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Ingår i: SCIENCE CHINA Materials. - : Springer Science and Business Media LLC. - 2095-8226 .- 2199-4501. ; 66:5, s. 2079-2089
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Tidskriftsartikel (refereegranskat)abstract
- Recently, cesium bismuth halide perovskites have emerged as potential substitutes to their counterparts, cesium lead halide perovskites, owing to their low toxicity. However, the photophysics of cesium-bismuth halides nanocrystals (NCs) have not yet been fully rationalized because their structures remain highly debated. The ultraviolet-visible (UV-vis) absorption along with other photophysical properties such as the nature and lifetime of the excited states vary considerably across the previous reports. Here, we successfully synthesize pure Cs3BiBr6 and Cs3Bi2Br9 NCs via a modified hot-injection method, where the structure can be easily controlled by tuning the reaction temperature. The UV-vis absorption spectrum of the pure Cs3Bi2Br9 NCs features two characteristic peaks originating from the absorption of the first exciton and second exciton, respectively, which ultimately clarifies the debate in the previous reports. Using femtosecond transient absorption spectroscopy, we systematically investigate the excited state dynamics of the Cs3Bi2Br9 NCs and reveal that the photoexcited carriers undergo a self-trapping process within 3 ps after excitation. More intriguingly, the Cs3Bi2Br9 NCs prepared by this method show much better photostability than those prepared by the ligand-assisted reprecipitation process. Photodetectors based on these Cs3Bi2Br9 NCs show a sensitive light response, demonstrating the definite potential for breakthrough optoelectronic applications. [Figure not available: see fulltext.].
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| 16. |
- Ghosh, Supriya, et al.
(författare)
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Slower Auger Recombination in 12-Faceted Dodecahedron CsPbBr3 Nanocrystals
- 2023
-
Ingår i: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 14:4, s. 1066-1072
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Tidskriftsartikel (refereegranskat)abstract
- Over the past two decades, intensive research efforts have been devoted to suppressions of Auger recombination in metal-chalcogenide and perovskite nanocrystals (PNCs) for the application of photovoltaics and light emitting devices (LEDs). Here, we have explored dodecahedron cesium lead bromide perovskite nanocrystals (DNCs), which show slower Auger recombination time compared to hexahedron nanocrystals (HNCs). We investigate many-body interactions that are manifested under high excitation flux density in both NCs using ultrafast spectroscopic pump-probe measurements. We demonstrate that the Auger recombination rate due to multiexciton recombinations are lower in DNCs than in HNCs. At low and intermediate excitation density, the majority of carriers recombine through biexcitonic recombination. However, at high excitation density (>1018 cm-3) a higher number of many-body Auger process dominates over biexcitonic recombination. Compared to HNCs, high PLQY and slower Auger recombinations in DNCs are likely to be significant for the fabrication of highly efficient perovskite-based photonics and LEDs.
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| 17. |
- Guo, Ruiqi, et al.
(författare)
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Exploiting Flexible Memristors Based on Solution-Processed Colloidal CuInSe2 Nanocrystals
- 2020
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Ingår i: Advanced Electronic Materials. - : Wiley. - 2199-160X. ; 6:5
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Tidskriftsartikel (refereegranskat)abstract
- Compared to analogous bulk materials, colloidal nanocrystals have presented a powerful platform for building up electronic devices on the nano/micrometer scale and flexible portable electronic apparatus with the benefits of solution-based processing approach at room temperature. Herein, memristors based on CuInSe2 (CISe) colloidal nanocrystals prepared using a solution-based process at room temperature are constructed. The memristors exhibit obvious bipolar resistive switching performance with a high–low resistance ratio larger than 5.7 and a steady retention time over 104 s. This is attributed to the copper ion redox reaction and the migration of these ions under an applied electric field. When the SET voltage is reached, the ions are separated from one of the electrodes, and the memristor changes from a low-resistance state (LRS) to a high-resistance state (HRS). Conversely, when the voltage reaches the RESET voltage, the memristor switches from a HRS to a LRS. In addition, the flexible memristor can be fabricated by spincoating nanocrystal solution onto polyethylene terephthalate (PET) at room temperature, showing excellent reproducibility of the performance including 100 times of continuous operation, 104 s of reproducible reading, 600 times of antifatigue testing, and thermal stability up to 95 °C. The flexible devices demonstrate promising applications for portable electronic devices.
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| 18. |
- Guo, Ruiqi, et al.
(författare)
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Manganese doped eco-friendly CuInSe2 colloidal quantum dots for boosting near-infrared photodetection performance
- 2021
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Ingår i: Chemical Engineering Journal. - : Elsevier BV. - 1385-8947. ; 403
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Tidskriftsartikel (refereegranskat)abstract
- CuInSe2 (CISe) colloidal quantum dots (QDs) display promising applications in photodetection especially within near-infrared (NIR) regions due to their high extinction coefficient and environmental-friendly. However, the high trap density and poor crystal quality introduced by the ternary structure result in low photodetection of CISe QDs devices. Herein, we dope transition metal manganese ions (Mn2+) into CISe QDs to tackle the above problems. Structural characterization results demonstrate the crystal quality of CISe QDs is improved by doping Mn2+ during the synthesis of QDs. The transient absorption (TA) spectroscopic study together with the space-charge-limited current (SCLC) measurements show the charge carrier lifetime of Mn-CISe QDs is much longer than that of the CISe QDs, due to the Mn2+ doping state serve as hole capturer forming a charge-compensated pair with the Cu2+ defect that makes the long-lived Cu2+ radiative recombination dominate. Furthermore, Mn2+ doping concurrently modifies the conduction band minimum and valence band maximum level of the QDs verified by the ultraviolet photoelectron spectroscopy (UPS), which determines the driving force for charge carrier transfer to acceptors. The optimal Mn2+ doping level (0.01 Mn:Cu feed ratio) balanced the above two factors in the QDs. The detector based on such Mn-CISe QDs exhibits responsivity of 30 mA/W and specific detectivity of 4.2 × 1012 Jones at near-infrared wavelength, the response speed of 0.76 µs, and suppressed dark current density of 1.6 × 10−10 A cm−2.
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| 19. |
- Hattori, Yocefu, et al.
(författare)
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Phonon-Assisted Hot Carrier Generation in Plasmonic Semiconductor Systems
- 2021
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Ingår i: Nano Letters. - : American Chemical Society (ACS). - 1530-6984 .- 1530-6992. ; 21:2, s. 1083-1089
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Tidskriftsartikel (refereegranskat)abstract
- Plasmonic materials have optical cross sections that exceed by 10-fold their geometric sizes, making them uniquely suitable to convert light into electrical charges. Harvesting plasmon-generated hot carriers is of interest for the broad fields of photovoltaics and photocatalysis; however, their direct utilization is limited by their ultrafast thermalization in metals. To prolong the lifetime of hot carriers, one can place acceptor materials, such as semiconductors, in direct contact with the plasmonic system. Herein, we report the effect of operating temperature on hot electron generation and transfer to a suitable semiconductor. We found that an increase in the operation temperature improves hot electron harvesting in a plasmonic semiconductor hybrid system, contrasting what is observed on photodriven processes in nonplasmonic systems. The effect appears to be related to an enhancement in hot carrier generation due to phonon coupling. This discovery provides a new strategy for optimization of photodriven energy production and chemical synthesis.
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| 20. |
- Hattori, Yocefu, et al.
(författare)
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Role of the Metal Oxide Electron Acceptor on Gold-Plasmon Hot-Carrier Dynamics and Its Implication to Photocatalysis and Photovoltaics
- 2021
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Ingår i: ACS Applied Nano Materials. - : American Chemical Society (ACS). - 2574-0970. ; 4:2, s. 2052-2060
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Tidskriftsartikel (refereegranskat)abstract
- The recent discovery that metal nanoparticles can generate hot carriers upon light excitation is seen as a breakthrough in the fields of plasmonics and photonics. However, the high expectations for a plasmonic revolution in applications have been dampened by the ultrafast energy dissipation of surface plasmon polariton modes. While research aimed at suppressing loss mechanisms is still pursued, another research direction has emerged where charges are harnessed before they relax. Despite the effort, efficiencies of devices based on hot carriers harnessed from plasmonics are typically very low (a few percent), which is somehow paradoxical since efficiencies for electron injection efficiency have been reported to be in the range from 25% to 40% and hole injection up to 85%. This indicates that the low device performance relates to the undesirable charge back-transfer process, which happens in the picosecond time scale. In this context, we performed a comparative ultrafast spectroscopy investigation with gold nanoparticles in direct contact with different metal oxides, namely, TiO2, ZnO, SnO2, and Al:ZnO. Electron dynamics revealed the decisive role of metal/semiconductor interfaces and semiconductor electronic structure in electron injection efficiency and recombination, with significant implications to the fields of photocatalysis and photovoltaics.
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| 21. |
- He, Yanmei, et al.
(författare)
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Direct Observation of Size-Dependent Phase Transition in Methylammonium Lead Bromide Perovskite Microcrystals and Nanocrystals
- 2022
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Ingår i: ACS Omega. - : American Chemical Society (ACS). - 2470-1343. ; 7:44, s. 39970-39974
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Tidskriftsartikel (refereegranskat)abstract
- Methylammonium (MA) lead halide perovskites have been widely studied as active materials for advanced optoelectronics. As crystalline semiconductor materials, their properties are strongly affected by their crystal structure. Depending on their applications, the size of MA lead halide perovskite crystals varies by several orders of magnitude. The particle size can lead to different structural phase transitions and optoelectronic properties. Herein, we investigate the size effect for phase transition of MA lead bromide (MAPbBr3) by comparing the temperature-dependent neutron powder diffraction patterns of microcrystals and nanocrystals. The orthorhombic-to-tetragonal phase transition occurs in MAPbBr3microcrystals within the temperature range from 100 to 310 K. However, the phase transition is absent in nanocrystals in this temperature range. In this work, we offer a persuasive and direct evidence of the relationship between the particle size and the phase transition in perovskite crystals.
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| 22. |
- He, Yanmei, et al.
(författare)
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Nature of Self-Trapped Exciton Emission in Zero-Dimensional Cs2ZrCl6 Perovskite Nanocrystals
- 2023
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Ingår i: The Journal of Physical Chemistry Letters. - 1948-7185. ; 14:34, s. 7665-7671
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Tidskriftsartikel (refereegranskat)abstract
- Low dimensional perovskite-inspired materials with self-tapped exciton (STE) emission have stimulated a surge of cutting-edge research in optoelectronics. Despite numerous efforts on developing versatile low-dimensional perovskite-inspired materials with efficient STE emissions, there is little emphasis on the intrinsic dynamics of STE-based broad emission in these materials. Here, we investigated the excited state dynamics in zero-dimensional (0D) Cs2ZrCl6 nanocrystals (NCs) with efficient blue STE emission. By using femtosecond transient absorption (fs-TA) spectroscopy, the ultrafast STE formation process within 400 fs is directly observed. Then, the formed STEs relax to an intermediate STE state with a lifetime of ∼180 ps before reaching the emissive STE state with a lifetime of ∼15 μs. Our work offers a comprehensive and precise dynamic picture of STE emission in low-dimensional metal halides and sheds light on extending their potential applications.
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| 23. |
- Honarfar, Alireza, et al.
(författare)
-
Photoexcitation dynamics in electrochemically charged CdSe quantum dots : From hot carrier cooling to auger recombination of negative trions
- 2020
-
Ingår i: ACS Applied Energy Materials. - : American Chemical Society (ACS). - 2574-0962. ; 3:12, s. 12525-12531
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Tidskriftsartikel (refereegranskat)abstract
- Fulfilling the potential of colloidal semiconductor quantum dots (QDs) in electrically driven applications remains a challenge largely since operation of such devices involves charged QDs with drastically different photophysical properties compared to their well-studied neutral counterparts. In this work, the full picture of excited state dynamics in charged CdSe QDs at various time scales has been revealed via transient absorption spectroscopy combined with electrochemistry as a direct manipulation tool to control the negative charging of CdSe QDs. In trions, excited states of single charged QDs, the additional electron in the conduction band speeds up the hot electron cooling by enhanced electron-electron scattering followed by charge redistribution and polaron formation in a picosecond time scale. The trions are finally decayed by the Auger process in a 500 ps time scale. Double charging in QDs, on the other hand, decelerates the polaron formation process while accelerates the following Auger decay. Our work demonstrates the potential of photoelectrochemistry as a platform for ultrafast spectroscopy of charged species and paves the way for further studies to develop comprehensive knowledge of the photophysical processes in charged QDs more than the well-known Auger decay, facilitating their use in future optoelectronic applications.
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| 24. |
- Honarfar, Alireza, et al.
(författare)
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Ultrafast Spectroelectrochemistry Reveals Photoinduced Carrier Dynamics in Positively Charged CdSe Nanocrystals
- 2021
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 125:26, s. 14332-14337
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Tidskriftsartikel (refereegranskat)abstract
- Extra charges in semiconductor nanocrystals are of paramount importance for their electrically driven optoelectronic and photovoltaic applications. Optical excitations of such charged nanocrystals lead to rapid recombinationviaan Auger process, which can deteriorate the performance of the corresponding devices. While numerous articles report trion Auger processes in negatively charged nanocrystals, optical studies of well-controlled positive charging of nanocrystals and detailed studies of positive trions remain rare. In this work, we used electrochemistry to achieve positive charging of CdSe nanocrystals, so-called quantum dots (QDs), in a controlled way. Femtosecond transient absorption spectroscopy was applied forin situinvestigation of the charge carrier dynamics after optical excitation of the electrochemically charged QD assembly on TiO2. We observe that without bias (i.e., neutral QDs), sub-picosecond hot carrier cooling is followed by multiple phases of the dynamics corresponding to electron injection and transfer to the TiO2. Positive charging first leads to activation of the hole traps close to the valence band maximum, which opens a rapid recombination channel of the optical excitation. A further increase in the positive bias interrupts the electron injection to TiO2, and if nanocrystals are positively charged, it leads to Auger relaxation in a few hundred picosecond timescale. This study represents a step toward the understanding of the effect of positive charging on the performance of semiconductor nanocrystals under conditions which closely mimic their potential applications.
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| 25. |
- Ji, Jingjing, et al.
(författare)
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Developing Halogen-Free Polymer Donors for Efficient Nonfullerene Organic Solar Cells by Addition of Highly Electron-Deficient Diketopyrrolopyrrole Unit
- 2021
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Ingår i: Solar RRL. - : Wiley. - 2367-198X. ; 5:5
-
Tidskriftsartikel (refereegranskat)abstract
- High-performance polymer donors when paired with nonfullerene acceptors are mainly limited to flanking halogenated benzodithiophene (BDT)-based π-conjugated copolymers, which however involve complex synthetic procedures. Herein, a series of halogen-free polymer donors that link BDT moiety with two highly electron-deficient benzodithiophene-dione (BDD) and diketopyrrolopyrrole (DPP) units with various molar ratios is developed. Compared with the benchmark PBDB-T donor containing BDD unit, additional incorporation of a stronger electron-negative DPP unit markedly lowers frontier molecular orbital levels and extends optical absorption, potentially leading to simultaneously enhanced VOC and JSC in organic solar cells. A remarkable power conversion efficiency (PCE) of 10.28% is thus obtained in the optimal P75 (BDD : DPP = 3:1 mol%) and Y6 blend cells in comparison with the reference PBDB-T:Y6 (9.20%). A slight addition of PC71BM into the blend is found to further generate finer phase-separated domains and thus increase the best efficiency up to 12.20%. The subtly critical roles of PC71BM are determined by transient absorption measurements on both thin-film and in situ devices to be the prolonged free charge carrier lifetime and the shallow charge transfer states, which enhance JSC and fill factor in the device, respectively.
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| 26. |
- Kang, Fengwen, et al.
(författare)
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Spectral Tuning, Stabilities under External Exposures, and Spontaneous Enhancement of Emission Intensity in Grown-into-Glass All-Inorganic Metal Halide Perovskite Nanocrystals
- 2023
-
Ingår i: Laser and Photonics Reviews. - : Wiley. - 1863-8880 .- 1863-8899. ; 17:1
-
Tidskriftsartikel (refereegranskat)abstract
- Herein, the grown-into-glass (GIG) CsPbBr3:Ln3+ (Ln = La, Lu) nanocrystals (NCs) are designed and fabricated using an in situ nanocrystallization method. It is shown that a substitution of Pb2+ sites with Ln3+ ions leads to a blueshift of emission position induced by an increase of the bandgap of CsPbBr3. Additionally, the GIG-samples are found to feature excellent photoluminescent (PL) properties after being immersed respectively in water for 300 days at room temperature, boiling water for 12 h, and corrosive environments for 24 h, as well as recoverable PL intensity either after several cycles of heat-cooling experiments or after being continuously exposed to a 405 nm laser irradiation. Besides, a spontaneous enhancement of 20-25% of emission intensity during the 1-2.5 hours' stage of a 405 nm laser irradiation, attributed to the radiative recombination of charge carriers that can be de-trapped from trapping levels upon the laser light irradiation and that then spontaneously reinforces the emission intensity, is observed in the GIG-CsPbBr3:Ln3+ NCs. Finally, a white light-emitting prototype, with a CIE chromaticity coordinate at (0.4110, 0.3706), a color rendering index of 89 and a correlated color temperature of 3363 K is realized by combining the GIG-CsPbBr3 NCs, YAG:Ce and CaWO4:Eu phosphors.
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| 27. |
- Lan, Zhenyun, et al.
(författare)
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Exploring the Intrinsic Point Defects in Cesium Copper Halides
- 2021
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 125:2, s. 1592-1598
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Tidskriftsartikel (refereegranskat)abstract
- Cesium copper halides Cs3Cu2X5 (X = Cl, Br, and I) have attracted much attention for optoelectronic applications because of their self-trap excitons and high photoluminescence quantum yield. Intrinsic point defects play a critical role in the optoelectronic performance of these materials by affecting fundamental properties, such as carrier mobility, lifetime, and recombination rate. In this work, we have calculated, by means of quantum mechanical calculations, formation energies and transition levels of all possible intrinsic point defects in Cs3Cu2X5. We have found that only Xi and XCs defects show simultaneously, deep transition energy levels and negative formation energies. Interestingly, the dominant defect under halide-rich growth conditions exhibits much higher concentration than that under halide-poor conditions. Thus, avoiding the halide-rich conditions could help in reducing the defect concentration.
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| 28. |
- Li, Chuanshuai, et al.
(författare)
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Electron Transfer Mediated by Iron Carbonyl Clusters Enhance Light-Driven Hydrogen Evolution in Water by Quantum Dots
- 2020
-
Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 13:12, s. 3252-3260
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Tidskriftsartikel (refereegranskat)abstract
- Photocatalytic water splitting has become a promising strategy for converting solar energy into clean and carbon-neutral solar fuels in a low-cost and environmentally benign way. Hydrogen gas is such a potential solar fuel/energy carrier. In a classical artificial photosynthetic system, a photosensitizer is generally associated with a co-catalyst to convert photogenerated charge into (a) chemical bond(s). In the present study, assemblies consisting of CdSe quantum dots that are coupled with one of two molecular complexes/catalysts, that is, [Fe2S2(CO)6] or [Fe3Te2(CO)9], using an interface-directed approach, have been tested as catalytic systems for hydrogen production in aqueous solution/organic solution. In the presence of ascorbic acid as a sacrificial electron donor and proton source, these assemblies exhibit enhanced activities for the rate of hydrogen production under visible light irradiation for 8 h in aqueous solution at pH 4.0 with up to 110 μmol of H2 per mg of assembly, almost 8.5 times that of pure CdSe quantum dots under the same conditions. Transient absorption and time-resolved photoluminescence spectroscopies have been used to investigate the charge carrier transfer dynamics in the quantum dot/iron carbonyl cluster assemblies. The spectroscopic results indicate that effective electron transfer from the molecular iron complex to the valence band of the excited CdSe quantum dots significantly inhibits the recombination of photogenerated charge carriers, boosting the photocatalytic activity for hydrogen generation; that is, the iron clusters function as effective intermediaries for electron transfer from the sacrificial electron donor to the valence band of the quantum dots.
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| 29. |
- Li, Chuanshuai, et al.
(författare)
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Graphitic Carbon Nitride/CdSe Quantum Dot/Iron Carbonyl Cluster Composite for Enhanced Photocatalytic Hydrogen Evolution
- 2021
-
Ingår i: ACS Applied Nano Materials. - : American Chemical Society (ACS). - 2574-0970. ; 4:6, s. 6280-6289
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Tidskriftsartikel (refereegranskat)abstract
- A g-C3N4/CdSe quantum dot/[Fe2S2(CO)6] composite has been successfully constructed. The structure and chemical composition of the composite were investigated via, inter alia, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The ability of the assembly to act as a photocatalyst for proton reduction to form hydrogen gas was studied. With visible light irradiation for 4 h, the total H2 production catalyzed by the g-C3N4/CdSe quantum dot/[Fe2S2(CO)6] composite was found to be 9 times as high as a corresponding CdSe/[Fe2S2(CO)6] assembly and significantly higher than either the CdSe quantum dots or g-C3N4 alone. The g-C3N4 support/matrix was found to enhance the stability and efficiency of the CdSe quantum dot/iron carbonyl cluster assembly in the photocatalytic hydrogen evolution process. Results from recycling tests showed that the g-C3N4/CdSe quantum dot/[Fe2S2(CO)6] composite is a sustainable and robust photocatalyst, maintaining the same activity after three cycles. The photoinduced charge carrier transfer dynamics in the g-C3N4/CdSe quantum dot/[Fe2S2(CO)6] composite system has been investigated by transient absorption (TA) and time-resolved photoluminescence (TRPL) spectroscopies. The spectroscopic results indicate efficient hole transfer from the valence band of the excited CdSe quantum dots to the molecular iron carbonyl clusters and from the defect state of the quantum dots to g-C3N4 in the g-C3N4/CdSe quantum dot/[Fe2S2(CO)6] composite, which significantly inhibits the recombination of photogenerated charge carriers in CdSe quantum dots and boosts the photocatalytic activity and stability for hydrogen evolution. Energy transfer from g-C3N4 to the CdSe quantum dot/[Fe2S2(CO)6] assembly with a time constant of 0.7 ns also contributed to the charge transfer process.
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| 30. |
- Li, Guohui, et al.
(författare)
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Efficient heat dissipation perovskite lasers using a high-thermal-conductivity diamond substrate
- 2023
-
Ingår i: SCIENCE CHINA Materials. - : Springer Science and Business Media LLC. - 2095-8226 .- 2199-4501. ; 66:6, s. 2400-2407
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Tidskriftsartikel (refereegranskat)abstract
- Efficient heat dissipation that can minimize temperature increases in device is critical in realizing electrical injection lasers. High-thermal-conductivity diamonds are promising for overcoming heat dissipation limitations for perovskite lasers. In this study, we demonstrate a perovskite nanoplatelet laser on a diamond substrate that can efficiently dissipate heat generated during optical pumping. Tight optical confinement is also realized by introducing a thin SiO2 gap layer between nanoplatelets and the diamond substrate. The demonstrated laser features a Q factor of ∼1962, a lasing threshold of 52.19 µJ cm−2, and a low pump-density-dependent temperature sensitivity (∼0.56 ± 0.01 K cm2 µJ−1) through the incorporation of the diamond substrate. We believe our study could inspire the development of electrically driven perovskite lasers. [Figure not available: see fulltext.].
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| 31. |
- Li, Guohui, et al.
(författare)
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Localized Bound Multiexcitons in Engineered Quasi-2D Perovskites Grains at Room Temperature for Efficient Lasers
- 2023
-
Ingår i: Advanced Materials. - : Wiley. - 0935-9648 .- 1521-4095. ; 35:20
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Tidskriftsartikel (refereegranskat)abstract
- Reducing the excitation threshold to minimize the Joule heating is critical for the realization of perovskite laser diodes. Although bound excitons are promising for low threshold laser, how to generate them at room temperature for laser applications is still unclear in quasi-2D perovskite-based devices. In this work, via engineering quasi-2D perovskite PEA2(CH3NH3)n-1PbnBr3n+1 microscopic grains by the anti-solvent method, room-temperature multiexciton radiative recombination is successfully demonstrated at a remarkably low pump density of 0.97 µJ cm−2, which is only one-fourth of that required in 2D CdSe nanosheets. In addition, the well-defined translational momentum in quasi-2D perovskite grains can restrict the Auger recombination which is detrimental to radiative emission. Furthermore, the quasi-2D perovskite grains are favorable for increasing binding energies of excitons and biexcitons and so as the related radiative recombination. Consequently, the prepared phase quasi-2D perovskite film renders a threshold of room-temperature stimulated emission as low as 13.7 µJ cm−2, reduced by 58.6% relative to the amorphous counterpart with larger grains. The findings in this work are expected to facilitate the development of solution-processable perovskite multiexcitonic laser diodes.
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| 32. |
- Li, Yi, et al.
(författare)
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Promoting photocatalytic hydrogen evolution by modulating the electron-transfer in an ultrafast timescale through Mo-S6 configuration
- 2024
-
Ingår i: Journal of Materials Science and Technology. - 1005-0302. ; 193, s. 73-80
-
Tidskriftsartikel (refereegranskat)abstract
- Maximizing ultrafast electron-transfer kinetics in semiconductor is pivotal but challenging for high-efficiency solar-to-energy during the photocatalytic reaction process due to the intrinsic property of photocatalysts with low surface electron density. Herein, a model photocatalyst CdS@Mo is synthesized through a typical hydrothermal method for modulating the ultrafast electron-transfer to enhance the surface electron density. X-ray absorption fine spectra (XAFS) reveal that Mo is coordinated with S atoms to form a Mo-S6 configuration which is different from common MoS2 and Mo foil structures. Based on the femtosecond transient absorption spectra (fs-TAS), it is found that the formation of Mo-S6 configuration contributes to the fast decay of CdS signal and Mo-S6 signal reactivation, illustrating the ultrafast electron-transfer (∼2.2 ps) from CdS to Mo-S6 configuration, which achieves the enhanced electron density of photocatalyst surface. Finally, a holistic photocatalytic performance evaluation discloses that the growing of Mo-S6 configuration obviously improves the photocatalytic hydrogen evolution (PHE) efficiency of CdS from 28.5 to 47.5 mmol g–1 h–1 with a solar-to-hydrogen (STH) efficiency of 0.10 % which is seldomly discussed in the system containing sacrificial agents. This work opens a new path to modulate the surface electron density by tuning the ultrafast electron-transfer for enhancing reaction efficiency in electron-density-dependent systems.
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| 33. |
- Liang, Mingli, et al.
(författare)
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Electronic Structure and Trap States of Two-Dimensional Ruddlesden–Popper Perovskites with the Relaxed Goldschmidt Tolerance Factor
- 2020
-
Ingår i: ACS Applied Electronic Materials. - : American Chemical Society (ACS). - 2637-6113. ; 2:5, s. 1402-1412
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Tidskriftsartikel (refereegranskat)abstract
- Two-dimensional Ruddlesden–Popper perovskites (2D RPPs) have been considered as promising building blocks for optoelectronic applications owing to optical properties comparable to the ones of 3D perovskites, together with superior stability. In addition, the more flexible structure adopted by such perovskites leads to a relaxation of the Goldschmidt tolerance factor (τ) requirement. Herein, we compare the crystalline and electronic structures, as well as the photophysics of two 2D perovskite single crystals (n-BA)2(MA)2Pb3I10 (BMAPI) and (n-BA)2(EA)2Pb3I10 (BEAPI) (n-BA = n-butylamine) containing small A-cations (MA, methylammonium) and large A-cations (EA, ethylammonium), respectively. The latter presents a relaxed τ (τEA > 1) compared with the requirement of a stable phase in 3D perovskites (τ < 1). Such relaxed τ is beneficial from the structural flexibility of the long organic cation bilayer and the pronounced lattice distortions in the 2D perovskite structures. We further elucidate how the greater lattice distortions concurrently modulate the electronic structure as well as trap densities in these 2D RPPs. The electronic band gap (Eg) of BEAPI (2.08 ± 0.03 eV) is ∼0.17 eV larger than the one of BMAPI (1.91 ± 0.03 eV). This is mainly because of a shift in the valence band maximum associated with the expansion of the Pb–I bond length in BEAPI. In addition, the overall trap state densities for BMAPI and BEAPI are calculated to be ∼2.18 × 1016 and ∼3.76 × 1016 cm–3, respectively, as extracted from the time-resolved photoluminescence studies. The larger trap density in BEAPI can be attributed to the stronger interfacial lattice distortion that sets in when large EA cations are contained into the inorganic crystal lattice.
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| 34. |
- Liang, Mingli, et al.
(författare)
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Free Carriers versus Self-Trapped Excitons at Different Facets of Ruddlesden-Popper Two-Dimensional Lead Halide Perovskite Single Crystals
- 2021
-
Ingår i: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 12:20, s. 4965-4971
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Tidskriftsartikel (refereegranskat)abstract
- The physical origin of sub-band gap photoluminescence in Ruddlesden-Poppers two-dimensional (2D) lead halide perovskites (LHPs) is still under debate. In this paper, we studied the photoluminescence features from two different facets of 2D LHP single crystals: the in-plane facet (IF) containing the 2D inorganic layers and the facet perpendicular to the 2D layers (PF). At the IF, the free carriers (FCs) dominate due to the weak electron-phonon coupling in a symmetric lattice. At the PF, the strain accumulation along the 2D layers enhances the electron-phonon coupling and facilitates self-trapped exciton (STE) formation. The time-resolved PL studies indicate that free carriers (FCs) at the IF can move freely and display the trapping by the intrinsic defects. The STEs at the PF are not likely trapped by the defects due to the reduced mobility. However, with increasing STE density, the STE transport is promoted, enabling the trapping of STE by the intrinsic defects.
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| 35. |
- Liang, Mingli, et al.
(författare)
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Spatially Resolved Local Electronic Properties of 2D Lead Halide Perovskite Single Crystals Studied by X-Ray Photoemission Electron Microscopy
- 2023
-
Ingår i: Solar RRL. - : Wiley. - 2367-198X. ; 7:1
-
Tidskriftsartikel (refereegranskat)abstract
- Recently, research on the edge states of 2D lead halide perovskites (LHPs) has been attracting much attention. The lower-energy edge state (LES) is believed to provide an efficient pathway for the dissociation of photoexcited excitons. However, the mechanism of the LES formation remains controversial, and studies that establish precisely the local electronic properties are lacking. Herein, the first study of spatially resolved electronic structures in 2D LHP single-crystal flakes by X-ray photoemission electron microscopy is presented, specifically identifying the contribution from the edge area. The results show that blueshifts occur in the Pb 5d core-level peaks at the edge area compared to the interior area with much less difference in I 4d core-level peaks. The shift becomes more pronounced as n varies from 1 to 3 (≈0.2–1.0 eV). This phenomenon is attributed to the surface restructuring of the edge area induced by the release of mechanical strain through lattice expansion. This work provides an important reference on the origin of the LES of 2D LHPs and is beneficial for future optoelectronic device applications.
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| 36. |
- Lin, Wei Cheng, et al.
(författare)
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Effect of energy bandgap and sacrificial agents of cyclopentadithiophene-based polymers for enhanced photocatalytic hydrogen evolution
- 2021
-
Ingår i: Applied Catalysis B: Environmental. - : Elsevier BV. - 0926-3373. ; 298
-
Tidskriftsartikel (refereegranskat)abstract
- A library of donor-acceptor system consisting of cyclopentadithiophene-based polymer photocatalysts have been designed and synthesized. Among all photocatalysts, the active PCPDTBSO achieved hydrogen evolution rates of 24.6 mmol h–1 g–1 with apparent quantum yields of 8.7 % at 500 nm. More importantly, combined the results of photocatalytic efficiency, apparent quantum yield, the time-resolved fluorescence decay spectra, the steady-state photoluminescence spectra, and the transient absorption spectroscopy, and the oxidation potentials of sacrificial donors and protons reduction potentials in different pH values, we confirmed the concept that ascorbic acid is a suitable sacrificial donor for narrow bandgap polymers and triethylamine is a suitable sacrificial donor for wide bandgap polymers owing to the existence of the optimal thermodynamic driving force. We believed this study would be advantageous for the selection of photocatalysts and sacrificial donors for hydrogen production.
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| 37. |
- Lin, Weihua, et al.
(författare)
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Carrier Cooling in Lead Halide Perovskites : A Perspective on Hot Carrier Solar Cells
- 2024
-
Ingår i: ACS Energy Letters. - 2380-8195. ; 9:1, s. 298-307
-
Forskningsöversikt (refereegranskat)abstract
- The concept of hot carrier solar cells (HCSCs) has been proposed as a promising yet elusive path toward high-performance photovoltaics (PV), capable of surpassing the Shockley-Queisser limit by recycling energy that would otherwise be lost during thermalization. Lead halide perovskites (LHPs) have emerged as highly promising materials for PV applications. The reports of slow hot carrier (HC) cooling in these materials have ignited discussions of their potential in realizing HCSCs. Here we summarize the key findings regarding HC dynamics in LHPs, as revealed by numerous studies using advanced time-resolved spectroscopies. We also emphasize the interconnected mechanisms involved in HC cooling. In addition, we discuss the influence of nanostructuring on HC cooling dynamics in LHPs and suggest that two-dimensional LHPs, with their inherent quantum well structure, might exhibit modified phononic features and altered carrier-phonon coupling strength. We conclude by critically discussing the prospects for HCSCs, taking into account our current understanding of HC cooling and excitation conditions under sunlight.
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| 38. |
- Lin, Weihua, et al.
(författare)
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Combining two-photon photoemission and transient absorption spectroscopy to resolve hot carrier cooling in 2D perovskite single crystals : the effect of surface layer
- 2022
-
Ingår i: Journal of Materials Chemistry C. - : Royal Society of Chemistry (RSC). - 2050-7526 .- 2050-7534. ; 10:44, s. 16751-16760
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Tidskriftsartikel (refereegranskat)abstract
- We investigate hot carrier (HC) cooling in two-dimensional (2D) perovskite single crystals by applying two complementary ultrafast spectroscopy techniques - transient absorption (TA) and time-resolved two-photon photoemission (TR-2PPE) spectroscopies. TR-2PPE directly maps the hot electron distribution and its dynamics in the conduction band to the detected photoelectron distribution. While TR-2PPE selectively probes the upper layer of the material, TA provides information on the whole bulk. Two cooling regimes are resolved in both techniques. The fast timescale of 100-200 fs is related to the electron scattering by longitudinal optical (LO) phonons and the slow timescale of 3-4 ps corresponds to the LO phonon relaxation. The HC cooling dynamic of TA measurement has faster initial stage and higher starting temperature for the slower stage than in TR-2PPE measurements. Conclusions about spatial sensitivity of the cooling dynamics across the 2D perovskite single crystals constitute valuable information that can guide the future development of HC solar cells and thermoelectric applications based on 2D perovskites.
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| 39. |
- Liu, Siyu, et al.
(författare)
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Probing the Multiexcitonic Dynamics in CsPbI3 Nanocrystals across the Temperature-Induced Reversible Phase Transitions
- 2023
-
Ingår i: Advanced Energy Materials. - 1614-6832. ; 13:30
-
Tidskriftsartikel (refereegranskat)abstract
- CsPbI3 nanocrystals (CPI NCs) have become a trending research topic due to their impressive potential in functional optoelectronic devices and optical gain applications. Their optical responses are governed by carrier dynamics, which is greatly influenced by temperature and corresponding phase structure due to the effects of inherently electron-phonon coupling. Notably, CPI NCs have been identified to adopt an unexpectedly stable cubic phase from room temperature to liquid helium temperature. Here, using in situ cryogenic electron diffraction measurements, it is unambiguously demonstrated that CPI NCs undergo consecutive cubic-tetragonal-orthorhombic phase transitions from 298 to 100 K. The corresponding temperature-dependent multiexcitonic dynamics are investigated in each phase by combining time-resolved photoluminescence and transient absorption spectroscopy. In addition to the temperature dependency, the lifetime of both excitons and biexcitons evidently depends on the phase structures of the CPI NCs, highlighting the crucial effect of crystal structure on the carrier dynamics. Moreover, the biexciton binding energy increases with higher crystal symmetry due to the decrease of the dielectric constant. The findings shed light on the structural phase transition and its relationship to the carrier dynamics in all-inorganic perovskite NCs, which provides critical insight into the structure-performance relationship in CPI NCs for promising applications in optoelectronic devices.
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| 40. |
- Liu, Yang, et al.
(författare)
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Inorganic ligands-mediated hole attraction and surface structuralreorganization in InP/ZnS QD photocatalysts studied via ultrafast visibleand midinfrared spectroscopies
- 2022
-
Ingår i: SCIENCE CHINA Materials. - : Springer Science and Business Media LLC. - 2095-8226 .- 2199-4501. ; 65:9, s. 2529-2539
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Tidskriftsartikel (refereegranskat)abstract
- Photoinduced carrier dynamical processes dominate the optical excitation properties of photocatalysts and further determine the photocatalytic performance. In addition, as the electrons generally possess a faster transfer rate than holes, hole transfer and accumulation are critical, and they play the key efficiency-limiting step during the photocatalytic process. Therefore, a comprehensive understanding of the dynamics of photogenerated holes and their determining factors in the photocatalytic system is highly essential to rationalize the full catalytic mechanism and develop highly efficient photocatalysts, which have not yet been revealed. In this work, the photoinduced charge carrier dynamics in InP/ZnS quantum dots (QDs) capped with long-chain L-typed ligands (oleylamine) and inorganic ligands (sulfide ion (S2−)) were explored. Time-resolved photoluminescence and femtosecond transient-absorption spectroscopy unambiguously confirmed the ultrafast hole transfer from the InP core to S2− ligands. Moreover, by probing the bleach of vibrational stretching of the ligands with transient midinfrared absorption spectroscopy, the hole transfer time was determined to be 4.2 ps. The injected holes are long-lived at the S2− ligands (>4.5 ns), and they can remove electrostatically attached surfactants to compensate for the spatial charge redistribution. Finally, compared with other inorganic ligands such as Cl− and PO43−, S2− balances the ionic radii and net charge to ensure the optimal condition for charge transfer. Such observation rationalizes the excellent photocatalytic H2 evolution (213.6 µmol mg−1 within 10 h) in InP/ZnS QDs capped with S2− compared with those capped with other ligands and elucidates the role of surface ligands in the photocatalytic activity of colloidal QDs.
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| 41. |
- Meng, Jie, et al.
(författare)
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Atomic-Scale Observation of Oxygen Vacancy-Induced Step Reconstruction in WO3
- 2021
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 125:15, s. 8456-8460
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Tidskriftsartikel (refereegranskat)abstract
- As the most common type of defects in WO3, surface oxygen deficiencies have been widely investigated in terms of their structure as well as physicochemical properties. In general, oxygen vacancy on the surface may lead to the reconstruction of the surface structure due to the need for surface energy minimization, especially for the area with high oxygen vacancy concentration. However, such a phenomenon has not been directly demonstrated or observed from the experiment. In the paper, we observed such surface reconstruction in the step area or high-index facets in WO3 using the spherical aberration-corrected scanning transmission electron microscope (Cs-STEM) with atomic-scale resolution. This surface reconstruction results in a structure of 5-fold symmetry pentagonal columns, which is first reported. According to the DFT calculation, the formation energy of oxygen vacancy in the step edge is much lower than the smooth surface. Furthermore, the formation energy of oxygen vacancy in the higher index (110) facet is lower than the low index (100) and (010) facets. Our experimental results support these findings, i.e., that the reconstruction is pronounced in the step or high-index facets with a high concentration of oxygen vacancy. Therefore, the high concentration of oxygen vacancy in the step or high-index facet area contributes to the formation of pentagonal column structures. This work could provide a novel insight into the correlation between intrinsic defect and surface structure formation in these materials.
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| 42. |
- Meng, Jie, et al.
(författare)
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Effect of Submonolayer ZnS Shell on Biexciton Dynamics of Indium Phosphide Quantum Dots
- 2023
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Ingår i: Advanced Electronic Materials. - 2199-160X. ; 9:12
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Tidskriftsartikel (refereegranskat)abstract
- Understanding high-order biexciton dynamics is important for the use of semiconductor quantum dots (QDs) in optoelectronic devices. The core–shell structure can be used to modulate biexciton dynamics by varying the shell thickness and core–shell energy band alignment. In this study, the biexciton dynamics in an unconventional case in which each QD is encapsulated by a submonolayer shell are demonstrated. The result of a transient absorption spectroscopic study shows that InP/ZnS core/shell QDs with submonolayer shell coverage exhibit a prolonged Auger lifetime. However, the QD size dependence of the Auger recombination time features two constant distinct stages instead of the typical monotonic volume scaling law in conventional QDs. It is attributed to the tradeoff between the enlarged QD size and quantum-well confinement for the Auger processes. However, the abrupt change between the two stages is due to the change in the shell coverage. This study provides a reference for the application of core–shell QDs in optoelectronic devices in which full coverage of the shell is not achieved.
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| 43. |
- Meng, Jie, et al.
(författare)
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Modulating Charge-Carrier Dynamics in Mn-Doped All-Inorganic Halide Perovskite Quantum Dots through the Doping-Induced Deep Trap States
- 2020
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Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 11:9, s. 3705-3711
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Tidskriftsartikel (refereegranskat)abstract
- Transition-metal ion doping has been demonstrated to be effective for tuning the photoluminescence properties of perovskite quantum dots (QDs). However, it would inevitably introduce defects in the lattice. As the Mn concentration increases, the Mn dopant photoluminescence quantum yield (PLQY) first increases and then decreases. Herein the influence of the dopant and the defect states on the photophysics in Mn-doped CsPbCl3 QDs was studied by time-resolved spectroscopies, whereas the energy levels of the possible defect states were analyzed by density functional theory calculations. We reveal the formation of deep interstitials defects (Cli) by Mn2+ doping. The depopulation of initial QD exciton states is a competition between exciton-dopant energy transfer and defect trapping on an early time scale (<100 ps), which determines the final PLQY of the QDs. The present work establishes a robust material optimization guideline for all of the emerging applications where a high PLQY is essential.
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| 44. |
- Meng, Jie, et al.
(författare)
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Optimizing the quasi-equilibrium state of hot carriers in all-inorganic lead halide perovskite nanocrystals through Mn doping : fundamental dynamics and device perspectives
- 2022
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Ingår i: Chemical Science. - : Royal Society of Chemistry (RSC). - 2041-6520 .- 2041-6539. ; 13:6, s. 1734-1745
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Tidskriftsartikel (refereegranskat)abstract
- Hot carrier (HC) cooling accounts for the significant energy loss in lead halide perovskite (LHP) solar cells. Here, we study HC relaxation dynamics in Mn-doped LHP CsPbI3 nanocrystals (NCs), combining transient absorption spectroscopy and density functional theory (DFT) calculations. We demonstrate that Mn2+ doping (1) enlarges the longitudinal optical (LO)-acoustic phonon bandgap, (2) enhances the electron-LO phonon coupling strength, and (3) adds HC relaxation pathways via Mn orbitals within the bands. The spectroscopic study shows that the HC cooling process is decelerated after doping under band-edge excitation due to the dominant phonon bandgap enlargement. When the excitation photon energy is larger than the optical bandgap and the Mn2+ transition gap, the doping accelerates the cooling rate owing to the dominant effect of enhanced carrier-phonon coupling and relaxation pathways. We demonstrate that such a phenomenon is optimal for the application of hot carrier solar cells. The enhanced electron-LO phonon coupling and accelerated cooling of high-temperature hot carriers efficiently establish a high-temperature thermal quasi-equilibrium where the excessive energy of the hot carriers is transferred to heat the cold carriers. On the other hand, the enlarged phononic band-gap prevents further cooling of such a quasi-equilibrium, which facilitates the energy conversion process. Our results manifest a straightforward methodology to optimize the HC dynamics for hot carrier solar cells by element doping. This journal is
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| 45. |
- Naumova, Maria A., et al.
(författare)
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Exploring the light-induced dynamics in solvated metallogrid complexes with femtosecond pulses across the electromagnetic spectrum
- 2020
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Ingår i: The Journal of chemical physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 152:21
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Tidskriftsartikel (refereegranskat)abstract
- Oligonuclear complexes of d4-d7 transition metal ion centers that undergo spin-switching have long been developed for their practical role in molecular electronics. Recently, they also have appeared as promising photochemical reactants demonstrating improved stability. However, the lack of knowledge about their photophysical properties in the solution phase compared to mononuclear complexes is currently hampering their inclusion into advanced light-driven reactions. In the present study, the ultrafast photoinduced dynamics in a solvated [2 × 2] iron(II) metallogrid complex are characterized by combining measurements with transient optical-infrared absorption and x-ray emission spectroscopy on the femtosecond time scale. The analysis is supported by density functional theory calculations. The photocycle can be described in terms of intra-site transitions, where the FeII centers in the low-spin state are independently photoexcited. The Franck-Condon state decays via the formation of a vibrationally hot high-spin (HS) state that displays coherent behavior within a few picoseconds and thermalizes within tens of picoseconds to yield a metastable HS state living for several hundreds of nanoseconds. Systematic comparison with the closely related mononuclear complex [Fe(terpy)2]2+ reveals that nuclearity has a profound impact on the photoinduced dynamics. More generally, this work provides guidelines for expanding the integration of oligonuclear complexes into new photoconversion schemes that may be triggered by ultrafast spin-switching.
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| 46. |
- Naumova, Maria A., et al.
(författare)
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Nonadiabatic Charge Transfer within Photoexcited Nickel Porphyrins
- 2024
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Ingår i: Journal of Physical Chemistry Letters. - 1948-7185. ; 15:13, s. 3627-3638
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Tidskriftsartikel (refereegranskat)abstract
- Metalloporphyrins with open d-shell ions can drive biochemical energy cycles. However, their utilization in photoconversion is hampered by rapid deactivation. Mapping the relaxation pathways is essential for elaborating strategies that can favorably alter the charge dynamics through chemical design and photoexcitation conditions. Here, we combine transient optical absorption spectroscopy and transient X-ray emission spectroscopy with femtosecond resolution to probe directly the coupled electronic and spin dynamics within a photoexcited nickel porphyrin in solution. Measurements and calculations reveal that a state with charge-transfer character mediates the formation of the thermalized excited state, thereby advancing the description of the photocycle for this important representative molecule. More generally, establishing that intramolecular charge-transfer steps play a role in the photoinduced dynamics of metalloporphyrins with open d-shell sets a conceptual ground for their development as building blocks capable of boosting nonadiabatic photoconversion in functional architectures through “hot” charge transfer down to the attosecond time scale.
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| 47. |
- Naumova, Maria A., et al.
(författare)
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Revealing Hot and Long-Lived Metastable Spin States in the Photoinduced Switching of Solvated Metallogrid Complexes with Femtosecond Optical and X-ray Spectroscopies
- 2020
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Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 11:6, s. 2133-2141
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Tidskriftsartikel (refereegranskat)abstract
- An atomistic understanding of the photoinduced spin-state switching (PSS) within polynuclear systems of d4-d7 transition metal ion complexes is required for their rational integration into light-driven reactions of chemical and biological interest. However, in contrast to mononuclear systems, the multidimensional dynamics of the PSS in solvated molecular arrays have not yet been elucidated due to the expected complications associated with the connectivity between the metal centers and the strong interactions with the surroundings. In this work, the PSS in a solvated triiron(II) metallogrid complex is characterized using transient optical absorption and X-ray emission spectroscopies on the femtosecond time scale. The complementary measurements reveal the photoinduced creation of energy-rich (hot) and long-lived quintet states, whose dynamics differ critically from their mononuclear congeners. This finding opens major prospects for developing novel schemes in solution-phase spin chemistry that are driven by the dynamic PSS process in compact oligometallic arrays.
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| 48. |
- Nguyen, Thinh Luong The, et al.
(författare)
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Molecular Linking Selectivity on Self-Assembled Metal-Semiconductor Nano-Hybrid Systems
- 2020
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Ingår i: Nanomaterials. - : MDPI. - 2079-4991. ; 10:7
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Tidskriftsartikel (refereegranskat)abstract
- Plasmonics nanoparticles gained prominence in the last decade in fields of photonics, solar energy conversion and catalysis. It has been shown that anchoring the plasmonics nanoparticles on semiconductors via a molecular linker reduces band bending and increases hot carriers' lifetime, which is essential for the development of efficient photovoltaic devices and photocatalytic systems. Aminobenzoic acid is a commonly used linker to connect the plasmonic metal to an oxide-based semiconductor. The coordination to the oxide was established to occur via the carboxylic functional group, however, it remains unclear what type of coordination that is established with the metal site. Herein, it is demonstrated that metal is covalently bonded to the linker via the amino group, as supported by Surface-Enhanced Resonant Raman and infrared spectroscopies. The covalent linkage increases significantly the amount of silver grafted, resulting in an improvement of the system catalytic proficiency in the 4-nitrophenol (4-NP) photoreduction.
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| 49. |
- Pan, Qinying, et al.
(författare)
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Ultrafast charge transfer dynamics in 2D covalent organic frameworks/Re-complex hybrid photocatalyst
- 2022
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 13:1
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Tidskriftsartikel (refereegranskat)abstract
- Rhenium(I)-carbonyl-diimine complexes have emerged as promising photocatalysts for carbon dioxide reduction with covalent organic frameworks recognized as perfect sensitizers and scaffold support. Such Re complexes/covalent organic frameworks hybrid catalysts have demonstrated high carbon dioxide reduction activities but with strong excitation energy-dependence. In this paper, we rationalize this behavior by the excitation energy-dependent pathways of internal photo-induced charge transfer studied via transient optical spectroscopies and time-dependent density-functional theory calculation. Under band-edge excitation, the excited electrons are quickly injected from covalent organic frameworks moiety into catalytic RheniumI center within picosecond but followed by fast backward geminate recombination. While under excitation with high-energy photon, the injected electrons are located at high-energy levels in RheniumI centers with longer lifetime. Besides those injected electrons to RheniumI center, there still remain some long-lived electrons in covalent organic frameworks moiety which is transferred back from RheniumI. This facilitates the two-electron reaction of carbon dioxide conversion to carbon monoxide.
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| 50. |
- Tagliabue, Giulia, et al.
(författare)
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Ultrafast hot-hole injection modifies hot-electron dynamics in Au/p-GaN heterostructures
- 2020
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Ingår i: Nature Materials. - : Springer Nature. - 1476-1122 .- 1476-4660. ; 19:12, s. 1312-1318
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Tidskriftsartikel (refereegranskat)abstract
- A fundamental understanding of hot-carrier dynamics in photo-excited metal nanostructures is needed to unlock their potential for photodetection and photocatalysis. Despite numerous studies on the ultrafast dynamics of hot electrons, so far, the temporal evolution of hot holes in metal-semiconductor heterostructures remains unknown. Here, we report ultrafast (t < 200 fs) hot-hole injection from Au nanoparticles into the valence band of p-type GaN. The removal of hot holes from below the Au Fermi level is observed to substantially alter the thermalization dynamics of hot electrons, reducing the peak electronic temperature and the electron-phonon coupling time of the Au nanoparticles. First-principles calculations reveal that hot-hole injection modifies the relaxation dynamics of hot electrons in Au nanoparticles by modulating the electronic structure of the metal on timescales commensurate with electron-electron scattering. These results advance our understanding of hot-hole dynamics in metal-semiconductor heterostructures and offer additional strategies for manipulating the dynamics of hot carriers on ultrafast timescales. Photo-excited gold nanoparticles are shown to provide ultrafast and efficient hot-hole injection to the valence band of p-type GaN, substantially altering hot-electron dynamics in the nanoparticles and forming a basis to design hot-hole-based optoelectronics.
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